Mixtures of reactive dyes and their use

ABSTRACT

Reactive dye mixtures comprising a black or navy reactive dye and a reactive disazo dye. The reactive dye mixtures of the present invention are suitable for exhaust dyeing, printing, continuous dyeing or discharge printing of a blended or interwoven fabric of cellulose fibres or cellulose nylon blends. The compounds of the present invention display good level dyeing properties, good build up and excellent low nylon cross-dyeing.

This application is a divisional application of pending U.S. applicationSer. No. 09/793,625, filed Feb. 27, 2001, now U.S. Pat. No. 6,585,782.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to mixtures of reactive dyes, which areparticularly suitable for dyeing fabric materials. They display goodbuild-up, wash fastness, and levelness; especially low nyloncross-staining in blended and interwoven fabrics.

2. Description of the Related Art

To date it has been difficult to find a single reactive dye whichdisplays good build-up to heavy black shades. In order to gain goodbuild-up in black shades, a reactive dye composition, which contains anumber of reactive dye components, has been used.

One black reactive dye (for example, the following formula (I) blackreactive dye) as the major component is usually mixed

with red, orange, yellow or other shade reactive dyes to yield blackreactive dye compositions.

Black reactive dye compositions are already known from Japanese PatentLaid-open No. 58-160362, 63-178170, 1-315469, 2-73870, 2-202956,8-104822, and 8-253697, and U.S. Pat. Nos. 5,445,654, 5,611,821,5,780,602, 5,849,887, 5,931,974 and 6,127,700.

In order to achieve high quality fabric, a blended or interweave fabric,which contains two different fibers, has been produced and sold in themarket.

When dyeing the blended fabrics, problems can be encountered in off-tonedyeing because different fibres have different affinities for thedyestuffs. Especially when dyeing nylon/cellulose blended fabrics, it isdifficult to get a low nylon cross-staining product. Therefore it isnecessary to select appropriate dyestuffs when dyeing blended orinterwoven fabrics.

There are many black reactive dye compositions which can be chosen inthe market. However the black dye compositions with little nyloncross-staining always show poor properties in levelness and build-up.Conversely, black dye compositions with good properties in levelness andbuild up always stain nylon badly.

Therefore, there is a strong demand for a reactive black dye compositionhaving good dyeing properties and low nylon cross-staining.

SUMMARY OF THE INVENTION

It is one object of the present invention to provide a reactive blackdye composition that is suitable for use in exhaustion, printing,continuous dyeing or discharge printing of fibers to provide good dyeingproperties.

Other objects of the present invention are to provide a reactive dyecomposition, which has good build-up properties, wash fastness,wash-off, levelness and low nylon cross-staining of blended orinterwoven fabrics.

The reactive dye composition of present invention comprises: one ormore, such as one, two or three, disazo dyes conforming to component(A), one or more, such as one,two or three, disazo dyes conforming tocomponent (B) and optionally one or two monoazo dyes conforming tocomponent (C).

Component (A) is selected from disazo dyes which may be represented byformula (I) to formula (III),

wherein Y is —CH═CH₂ or —C₂H₄W, W is a leaving group which can beeliminated by a base; R₁, and R₂ are each independently hydrogen,methyl, ethyl, methoxy, ethoxy or sulfonic acid, preferably hydrogen ormethoxy, and most preferably hydrogen. The leaving group W is forexample, —Cl, —Br, —F, —OSO₃H, —SSO₃H, —OCO—OCH₃, —OPO₃H₂, —OCO—C₆H₅,—OSO₂—(C₁-C₄-alkyl) or —OSO₂—N(C₁-C₄-alkyl)₂. W is preferably —Cl,—OSO₃H, —SSO₃H, —OCO—CH₃, —OCO—C₆H₅ or —OPO₃H₂, more preferably —Cl or—OSO₃H and, particularly preferably, —OSO₃H.

Component (B) is selected from the reactive disazo dye which may berepresented by formula (IV) to formula (XI),

wherein Y, R₁, and R₂ are defined as the above; R₃ and R₄ are eachindependently hydrogen, methyl, ethyl, methoxy, ethoxy or sulfonic acid,preferably hydrogen or methoxy, particularly preferably hydrogen; R₅ isamino, —NHC₂H₄COOH or —NHCOCH₃; R₆ is methyl, ethyl, propyl orcarboxylic acid; R₇ is amino, —NHC₂H₄COOH, —NHCONH₂ or —NHCOCH₃; R₈, andR₉ are each independently hydrogen, amino or sulfonic acid; and R₁₀ is—CH₂SO₃H or —CONH₂.

Furthermore, the reactive black dye composition of the present inventioncan contain component (C) with at least a reactive monoazo dye offormula (15), (16) or (17).

The dyestuffs of the present invention all contain anionic groups, suchas a sulfonic acid groups: for convenience they are depicted as freeacid in the specification. When the dyestuffs of the present inventionare manufactured, purified or used, they exist in the form of watersoluble salts, especially alkaline metallic salts, such as sodium salts,potassium salts or ammonium salts.

The ratio of each dye component can be changed over a wide range. Ingeneral, the minimum relative weight percentage for each dye componentis 3%, and the maximum relative weight percentage is 90%. The dyecomposition of the present invention preferably contains component (A)30˜80% by weight, component (B) 25˜75% by weight, and optionallycomponent (C) 0˜45% by weight.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The compounds represented by formula (I) of the present invention can besynthesized by the following method.

First, the diazonium salt derived from the amine of the formula (a)

wherein Y, which is defined as the above, is coupled with compound (b)

under acidic conditions. The monoazo compound thus obtained is thenreacted with a diazonium salt, derived from an aromatic amine (c),

wherein Y, R₁, and R₂ are defined as above under a basic conditions toyield a compound of formula (I).

Examples of formula (I) are formula (1), formula (2) or formula (3).

The compound of formula (II) can be synthesized by the following method.

First the tetrazonium salt derived from the aromatic diamine (d)

is coupled with a compound of formula (b) under acidic conditions. Thecompound thus obtained is then reacted with the diazonium salt derivedfrom the amine (c) under basic conditions, to yield a compound offormula (II).

An example of formula (II) is formula (4).

Compounds of formula (III) of the present invention can be synthesizedby the following method.

First, the compound of formula (e) is condensed with compound of formula(f).

The resulting product is diazotised and the diazonium salt thus obtainedis coupled with a compound of formula (b), under acidic conditions, thencoupled with the diazonium salt derived from amine (g), under basicconditions. Finally it is condensed with a compound of formula (h) toyield a compound of formula (III), wherein Y is defined as above.

An example of a compound of formula (III) is a compound of formula (5).

Compounds of formula (IV) and formula (V) of the present invention, canbe synthesized by the following method. The diazonium salt derived froman amine (c) is coupled with a compound of formula (i),

the resulting monoazo derivative is then diazotised and coupled with acompound of formula (j) or a compound of formula (k),

wherein R₆ is defined as the above.

Examples of compound of formula (IV) and (V) are formula (6) and

Compounds of formula (VI) and (VIII) can be synthesized by the followingmethod.

The diazonium salt derived from amine (c) is coupled with a compound offormula (m), and the resulting monoazo derivative is

then diazotised. The diazonium salt thus obtained is coupled with acompound of formula (k) or (j).

Examples of formula (VI) are formula (8), (9) and an example of formula(VIII) is formula (10).

Formula (VII), (IX) and (XI) of the present invention can be synthesizedby the following method.

The diazonium salt derived from amine (c) is coupled with a compound offormula (n)

wherein R₅ is defined as above, and the resulting monoazo derivative isdiazotised. The diazonium salt thus obtained is coupled with a compoundsof formula (o), (p) or (q).

wherein R₃, R₄, R₆, R₇, R₈, R₉ and R₁₀ are defined as the above.

Examples of formula (VII), (IX) and (XI) are formulae (11), (12) and(13) respectively.

Compounds of formula (X) can be synthesized by the following method.

The diazonium salt derived from amine (s) is coupled with a compound offormula (o), then hydrolyzed in aqueous alkali at refluxing, to yield acompound of formula (t),

wherein R₅, R₇, R₈ and R₉ are defined as above. Finally, the compound offormula (t) is coupled with a diazonium salt derived from an amine (c).

An example of formula (X) is formula (14).

The compositions of the present invention can be prepared in many ways.For example, by using separately prepared dye components and mixingtogether to make powder, granular or liquid form, or by mixing a numberof individual dyes as a dyeing recipe in a dye house. The dye mixturesof this invention can be prepared, for example, by mixing theindividuals dyes. The mixing process is carried out, for example, in asuitable mill, e.g. in a ball mill, pin mill, or in kneaders or mixers.If the dyestuff mixtures of the invention are prepared by mechanicalmixing of the individual dyestuffs, any necessary standardizing agents,dust removal agents or further auxiliaries, which are customary indyeing, and are customary in dyestuff preparations, used in this contextare added during mixing.

The dyestuffs of present invention can be in the form of powders,granules or liquids; and an auxiliary agent, for example, a retardingagent, leveling agent, assistant agent, surfactant, or dispersing agentmay be added.

The dye compositions of the present invention can be in solid or inliquid form. In the solid form, they may generally contain electrolytesalts customary for water-soluble and in particular fiber-reactivedyestuffs, such as sodium chloride, potassium chloride and sodiumsulfate. Furthermore they can contain auxiliaries customary incommercial dyestuffs, such as buffer substances, which are capable ofestablishing a pH in aqueous solution of between 3 and 7, such as sodiumacetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate,and disodium hydrogen phosphate or agents which improve the solubility,such as known naphthalenesulfonic acid-formaldehyde condensationproducts, methylnaphthalenesulfonic acid-formaldehyde condensationproducts, acetylaminonaphthol based compounds, etc. If they are liquid,aqueous solution (including the content of thickeners, such as arecustomary in printing pastes), they may contain dissolved theabove-mentioned substances and may contain substances which ensure thestorage stability of these preparations, such as mould-preventingagents.

The ratio of each dye component can be changed over a wide range. Ingeneral, the minimum relative weight percentage for each dye componentis 3%, and the maximum relative weight percentage is 90%. The dyecomposition of the present invention preferably contains component (A)30˜80% by weight, component (B) 25˜75% by weight, and optionallycomponent (C) 0˜45% by weight.

The black dye compositions of the present invention can be used to dye awide range of natural and synthetic fibres which contain either amino orhydroxyl groups, such as wool, silk and synthetic polyamides. These dyecompositions can also be used to dye natural cellulosic fibres such ascotton, linen, ramie, jute as well as regenerated cellulosic fibres. Thedyeing method used is the one generally used when a reactive dyestuff isapplied to the appropriate substrate. In the case of dyeing cellulose,the substrate is added to an aqueous bath containing the required amountof inorganic electrolyte (common salt or sodium sulfate) to achieve ahigh level of exhaustion. The covalent bond, connecting the dye to thecellulosic fibre, is formed on the addition of alkali (soda ash, sodiumbicarbonate or caustic soda).

The black dye composition of the present invention is of high industrialimportance. It allows level, heavy (deep black) shades to be obtainedwith minimal amounts of cross staining of polyamide when dyeing acotton/nylon blend.

Many examples have been used to illustrate the present invention. Theexamples sited below should not be taken as a limit to the scope of thecurrent invention. In these examples, the compound is represented by thefree acid. However, in practice, it will exist as a (metal) salt, forexample as the sodium, lithium, potassium or ammonium salt, particularlythe sodium salt. In the following examples, quantities are given asparts by weight (%) and temperature are given in degree Celsius.

EXAMPLE 1

Formulate a mixture using 32.65 parts of dye of formula (1), 24.49 partsof dye formula (6) and 42.86 parts of dye of formula (15). The followingdyeing processes were carried out.

(1) Exhaust Dyeing on Cotton

a) Materials

Bleached, unmercerised woven cotton (4 gm), Glaubers salt solution (240g/l), soda ash solution (100 g/l), dilute acetic acid (10 g/l).

b) Dyeing Parameters

Depth of shade: 4% on weight of cotton

Liquor ratio: 20:1

Glaubers salt concentration: 60 g/l

Soda ash concentration: 20 g/l

c) Dyeing Procedure

1. Take 1 part of the above dye composition and dissolve in 100 parts ofdistilled water.

2. To a dyeing vessel containing 16 ml of the above dye solution, 20 mlsof Glaubers salt solution and 28 mls of distilled water, add a 4 gmpiece of bleached unmercerised cotton.

3. Place the sealed dyeing vessel in a thermostatically controlled bathand heat from room temperature to 60° C. at approx. 5° C./minute.Maintain the dyeing vessel at this temperature for 30 minutes.

4. Add 16 ml of soda ash solution to the dyeing vessel and return to thethermostatically controlled bath for a further 60 mins at 60° C.

5. Remove the dyed cotton from the dyeing vessel and rinse well withcold water to remove chemicals and (some) loose colour.

6. Rinse the dyed fabric in a solution of dilute acetic acid for 2minutes in order to neutralise any, ‘carry over’ of alkali from thedyeing process.

7. Treat the dyed cotton for 15 min. in boiling water containing 2 g/lof an anionic detergent.

8. Rinse the cotton in warm water (60° C.), and then in cold water,(each for 2 minutes) and dry.

9. Assess the shade on the cotton.

2. Nylon Staining Test

(a) Materials

Bleached unmercerised woven cotton (4 gm), knitted nylon (1 gm) andnylon taffeta (1 gm).

(b) Dyeing Parameters

Depth of shade:4% on weight of cotton

Glaubers salt concentration 60 g/l

Soda ash concentration 20 g/l

(c) Dyeing Procedure

The same procedure was adopted as previously described, although thedyebath (final volume of 80 ml) contained samples of cotton (4 gm),knitted nylon (1 gm) and nylon taffeta (1 gm).

(d) Estimation of Nylon Staining

Assess the staining on the nylon fabric spectrophotometrically.

EXAMPLES 2-20

A series of different mixtures were formulated and dyed on cotton, usingthe procedure previously described in example 1, to yield deep blackshades. The composition of the formulations-are shown in Table 1.

The same formulations were also used to dye a mixture of cotton (4 gm)and nylon (2×1 gm) as described in the ‘nylon staining test’. The amountand shade of the nylon staining is shown in Table 2. A commerciallyavailable reactive black formulation, known to give significant amountsof undesirable orange staining of the nylon was used as a control in thestudy.

The lower the value of ‘chroma’ (Table 2), the lower is the amount ofnylon staining exhibited by a dyestuff formulation. A formulationexhibiting a small amount of on-tone (grey) staining of the nylon ishighly desirable to avoid the formation of an unlevel (‘skittery’)dyeing and give good fastness properties. Table 2 clearly shows that theblack dye compositions of the present invention show much superiortechnical performance (lower nylon cross-staining) than the existingcommercial product.

TABLE 1 COMPOSITION OF BLACK FORMULATIONS Component (A) Component (B)Component (C) Example Compound Compound Compound Compound No. ratioratio ratio ratio formula (1) formula (6) formula (13) — 41.32% 39.67%19.01% 3 formula (1) formula (11) — formula (15) 30.59% 29.41% 40.00% 4formula (1) formula (14) formula (11) — 38.83% 20.71% 40.45% 5 formula(1) formula (8) formula (11) — 61.16% 16.82% 22.02% 6 formula (1)formula (12) formula (11) — 38.83% 20.71% 40.45% 7 formula (1) formula(7) formula (11) — 53.33% 5.33% 41.33% 8 formula (1) formula (8) — —69.62% 30.38% 9 formula (1) formula (8) — formula (16) 61.16% 16.82%22.02% 10 formula (1) formula (7) — formula (16) 53.33% 5.33% 41.33% 11formula (1) formula (10) — formula (16) 56.52% 8.70% 34.78% 12 formula(1) formula (10) — formula (15) 40.00% 28.00% 32.00% 13 formula (1)formula (9) — formula (16) 34.48% 51.72% 13.79% 14 formula (1) formula(9) — formula (15) 41.82% 30.91 27.27% 15 formula (1) formula (10) —formula (16) 34.48% 51.72% 13.79% 16 formula (1) formula (13) formula(11) — 30.49% 60.98%  8.54% 17 formula (4) formula (12) formula (11) —56.56% 27.15% 16.29% 18 formula (5) formula (12) formula (11) — 40.00%25.00% 35.00% 19 formula (2) formula (12) formula (11) — 51.59% 19.48%28.57% 20 formula (3) formula (12) formula (11) — 50.63% 17.72% 31.65%

TABLE 2 SHADE OF NYLON IN NYLON STAINING TEST Dye composition ChromaShade of nylon Control 33.3 Orange (commercially available sampleExample 1  4.3 (Greenish-) Grey Example 2  6.1 Grey Example 3  2.6 GreyExample 4  5.9 Grey Example 5  4.4 (Reddish-) Grey Example 6  12.3 GreyExample 7  5.4 Grey Example 8  2.6 Grey Example 9  5.7 (Reddish-) GreyExample 10 13.2 Grey Example 11 10.2 Grey Example 12 4.3 (Bluish-) GreyExample 13 1.7 Grey Example 14 5.1 (Bluish-) Grey Example 15 6.8 GreyExample 16 4.5 (Greenish-) Grey Example 17 6.6 Grey Example 18 22.3(Reddish-) Grey Example 19 12.2 (Reddish-) Grey Example 20 12.4(Reddish-) Grey

The black dye composition of the present invention can be widely appliedto substrates containing a hydroxyl group by the traditional dyeingmethods such as exhaustion, printing and (semi-) continuous dyeing.

For cellulosic fibres, the black dye composition of the presentinvention is a dye composition with great industrial value. It has goodbuild-up properties (to yield heavy black shades), can be dyed in alevel/uniform manner, loose (hydrolysed) dye can be readily removed andexhibits good fastness properties. In particular, it exhibits minimalnylon cross-staining.

From the foregoing description, one skilled in the art can easilyascertain the essential characteristics of this invention, and withoutdeparting from the scope thereof, can make various changes andmodifications of the invention to adapt it to various usages andconditions. Thus, other embodiments are also within the claims.

What is claimed is:
 1. A reactive dye composition comprising: (A) areactive dye of the formula (I),

wherein Y is —CH═CH₂ or —C₂H₄W, W is a leaving group, R₁ and R₂ are eachindependently hydrogen, methyl, ethyl, methoxy, ethoxy or sulfonic acid;and (B) a disazo reactive dye of formula (VII) and optionally at leastone disazo reactive dye selected from the group consisting of theformula (IV), (V), (VI), (VIII), (X), and (XI),

wherein Y, R₁ and R₂ are defined as above; R₃ and R₄ are eachindependently hydrogen, methyl, ethyl, methoxy, ethoxy or sulfonic acid;R₅ is amino, —NHC₂H₄COOH or —NHCOCH₃; R₆ is methyl, ethyl, propyl orcarboxylic; R₇ is amino, —NHC₂H₄COOH, —NHCONH₂ or —NHCOCH₃; R₈ and R₉are each independently hydrogen, amino or sulfonic acid and R₁₀ is—CH₂SO₃H or CONH₂.
 2. A dye mixture according to claim 1, wherein saidcomponent (B) a disazo reactive dye of formula (VII) and comprising atleast one disazo reactive dyes selected from the group consisting of theformula (IV), (V), (VI), (VIII), (X), and (XI).
 3. A dye mixtureaccording to claim 1, wherein said W is —Cl, —Br, —F, —OSO₃H, —SSO₃H,—OCO—OCH₃, —OPO₃H₂, —OCO—C₆H₅, —OSO₂—(C₁-C₄ alkyl) or —OSO₂—N(C₁-C₄alkyl)₂.
 4. A dye mixture according to claim 1, wherein said W is —Cl,or —OSO₃H.
 5. A dye mixture according to claim 2, wherein said component(B) comprising the compound of formula (VII) and at least one disazoreactive dyes selected from the group consisting of the formula (IV),(V), (VI), (X), and (XI).
 6. The composition of claim 1, wherein saidcompound of formula (I) is the compound of formula (1)


7. The composition of claim 1, wherein said compound of formula (I) isthe compound of formula (2).


8. The composition of claim 1, wherein said compound of formula (I) isthe compound of formula (3).


9. The composition of claim 5, wherein said compound of formula (V) isthe compound of formula (7).


10. The composition of claim 5, wherein said compound formula (VI) isthe compound of formula (8).


11. The composition of claim 5, wherein said compound of formula (VII)is the compound of formula (11).


12. The composition of claim 5, wherein said the compound of formula(XI) is the compound of formula (13).


13. The composition of claim 5, wherein said compound of formula (X) isthe compound of formula (14).


14. The composition of claim 1 comprising component (A) 30% to 80% byweight and component (B) 20% to 70% by weight.
 15. The composition ofclaim 1 optionally comprising a component (C) is selected from thereactive monoazo dye group consisting of formula (12), formula (15),formula (16), and formula (17).


16. The composition of claim 15 comprising component (A) 30% to 80% byweight, component (B) 20% to 70% by weight, and component (C) 0% to 45%by weight.